US7960488B2 - Aluminoxane compositions, their preparation, and their use in catalysis - Google Patents
Aluminoxane compositions, their preparation, and their use in catalysis Download PDFInfo
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- US7960488B2 US7960488B2 US12/299,555 US29955507A US7960488B2 US 7960488 B2 US7960488 B2 US 7960488B2 US 29955507 A US29955507 A US 29955507A US 7960488 B2 US7960488 B2 US 7960488B2
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- 0 [2*]N1=C([3*])C([4*])=N([5*])C1(C)C Chemical compound [2*]N1=C([3*])C([4*])=N([5*])C1(C)C 0.000 description 2
- RAUFOFIIBYZYEY-UHFFFAOYSA-N CC1=N(C)C2(C)(C)N3=C1C=CC=C3/C(C)=N\2[Ar] Chemical compound CC1=N(C)C2(C)(C)N3=C1C=CC=C3/C(C)=N\2[Ar] RAUFOFIIBYZYEY-UHFFFAOYSA-N 0.000 description 1
- KELMTJAAHYZTHO-UHFFFAOYSA-N CN=C(C)(C)OC Chemical compound CN=C(C)(C)OC KELMTJAAHYZTHO-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
Definitions
- This invention relates to aluminoxane compositions that are of utility in formation of catalyst systems, to methods for the preparation of these aluminoxane compositions and catalyst systems, and to the use of such catalyst systems in the polymerization of olefin monomers, dienes, or the like.
- Aluminoxane compositions are widely used in combination with various types of metallocenes and transition metal compounds to prepare catalyst systems for polymerizing olefin monomers.
- certain limitations are associated with standard aluminoxane solutions, such as poor solubility, instability, and gel formation.
- solutions of conventional aluminoxanes, such as methylaluminoxane (MAO) must be kept at lower temperatures to inhibit degradation via irreversible gel formation.
- aluminoxanes with halogen added are generally more stable to precipitation than standard aluminoxanes, they are still nonetheless susceptible to some precipitation at room temperature (about 20° C.) and higher temperatures.
- the present invention provides aluminoxane compositions useful as activators with transition metal components in catalyzing the polymerisation of olefins.
- Aluminoxane compositions according to this invention comprise aluminoxane, halogen source, and Lewis base. Further details of the present invention are provided in the detailed description.
- composition derived from at least; a) aluminoxane source; b) halogen source; and c) Lewis base.
- the aluminoxane source can comprise methylaluminoxane.
- the halogen source can comprise fluorine source.
- the Lewis base can comprise one or more of multi-dentate donor and mono-dentate donor, including mixtures or combinations thereof; multi-dentate donor can comprise, e.g., siloxane; mono-dentate donor can comprise, e.g., NR 2 3 , wherein each R 2 is independently hydrogen atom or hydrocarbyl group having up to about 24 carbon atoms.
- Aluminoxane source can comprise about 0.5 mol % to about 15 mol % halogen atoms relative to Al atoms.
- Aluminoxane source can comprise about 0.8 mol % to about 15 mol %, or about 4.7 mol %, halogen atoms relative to Al atoms.
- the halogen source when the halogen source is dimethylaluminum fluoride, it can comprise up to about 30 mol % halogen atoms relative to Al atoms; when the halogen source is alpha,alpha,alpha-trifluorotoluene (TFT), it can comprise up to about 8 mol % halogen atoms relative to Al atoms.
- Compositions according to this invention can comprise about 0.5 mol % to about 15 mol % donor atoms from Lewis base relative to aluminum atoms. Also provided is composition derived from at least: a) aluminoxane source; and b) Lewis base that is also halogen source.
- Lewis base can comprise (i) NMeR 2 2 , wherein each R 2 is independently hydrogen atom or hydrocarbyl group having up to about 24 carbon atoms, or (ii) OMTS, or combinations of (i) and (ii).
- composition comprising combining at least a) aluminoxane source; b) halogen source; and c) Lewis base.
- the halogen source can comprise fluorine source.
- method of preparing composition comprising combining at least: a) aluminoxane source comprising up to about 30 mol % fluorine atoms relative to aluminum atoms; and b) Lewis base.
- Also provided is method of polymerizing monomer comprising combining composition of this Invention, transition metal component, and monomer.
- Aluminoxane source (A) can comprise any aluminoxane, including without limitation methylaluminoxane (MAO), ethylaluminoxane (EAO), isobutylaluminoxane (IBAO), other aluminoxanes, and combinations thereof, MAO may be derived from AlMe 3 and wafer; EAO may be derived from AlEt 3 and water; IBAO may be derived from Al i Bu 3 and water.
- MAO methylaluminoxane
- EAO ethylaluminoxane
- IBAO isobutylaluminoxane
- Halogen source (B) can comprise any halogen source, for example fluorine source, chlorine source, or bromine source.
- Halogen source (B) can comprise Lewis base.
- halogen source can refer to halogen atom in the negative state, generally referred to as halide ion, e.g., F ⁇ , Cl ⁇ , Br ⁇ .
- halogen source is commonly used in the art describe such halide ions.
- Halogen source (B) can comprise fluorine source, for example, alpha,alpha,alpha-trifluorotoluene.
- R can be a straight chain, branched, cycloalkyl, aryl, or araalkyl group.
- the hydrocarbyl group can be an aryl group, in halohydrocarbons in which all R are hydrogen atoms, such halohydrocarbons tend to react slowly with aluminoxane, and frequently the reaction does not go to completion, i.e., the yields can be low.
- a suitable type of halohydrocarbon is a tertiary halohydrocarbon: another suitable type of halohydrocarbon is that in which at least one R is an aryl group. Secondary and primary halohydrocarbons appear to provide less stability to the believed cationic species of the ionic aluminoxane complexes, or to the intermediate in the formation of the partially halogenated aluminoxane.
- halohydrocarbon is one in which at least one R is an aryl group, e.g., a phenyl group.
- the halohydrocarbon can be a primary halohydrocarbon in which one R is an aryl group and the other R(s) are hydrogen atoms, or all of the other substituents are halogen atoms.
- This group of halohydrocarbons can be represented by the formula: ArG n where Ar is an aromatic hydrocarbon ring system, which typically contains up to about 25 carbon atoms, or up to about 12 carbon atoms, or 6 carbon atoms in the ring system (i.e., excluding X and excluding any substituents that may be present on the ring(s)); G is —CX 3 , —CX 2 R, or —CXR 2 , in which X is, independently, a fluorine atom, chlorine atom, or bromine atom, and in which R is, independently, a hydrogen atom or C-m alkyl group; and n is 1 to 5, or 1 to 3, or 1 or 2, G can be a trihalomethyl group.
- Ar is an aromatic hydrocarbon ring system, which typically contains up to about 25 carbon atoms, or up to about 12 carbon atoms, or 6 carbon atoms in the ring system (i.e., excluding X and excluding any substituent
- substituents on the aromatic ring(s) other than hydrogen and the group(s) containing labile halogen atom(s) can be electron-donating substituents.
- Halogenation agents containing aromatic groups having electron-withdrawing substituents on the ring such as fluorine, were observed to have slower reaction rates than halogenation agents with aromatic groups having only hydrogen atoms as substituents.
- halogenation agents containing aromatic groups having electron-donating substituents were observed to have faster reaction rates than halogenaton agents in which there were only hydrogen atoms on the aromatic ring.
- Typical electron-donating substituents include hydrocarbyloxy groups and hydrocarbyl groups.
- Suitable halohydrocarbons having an aryl group include alpha,alpha,alpha-trifluorotoluene, alpha,alpha-difluorotoluene, alpha-fluorotoluene, octafluorotoluene, 1,2-di(fluoromethyl)benzene, 1,3-di(fluoromethyl)benzene, 1,4-di(fluoromethyl)benzene, 1,2-bis(difluoromethyl)benzenes 1,3-bis(difluoromethyl benzene, 1,4-bis(difluoromethyl)benzene, 1,3-bis(trifluoromethyl)benzene, 1,3,5-tris(trifluoromethyl)benzene, 4-methyl-1-(trifluoromethyl)benzene, 3-methyl-1-(trifluoromethyl)benzene, 1,3-bis(trifluoromethyl)-4-methylbenzene, 1,4-bis(
- Suitable halohydrocarbons which do not have an aryl group include tert-butyl fluoride (2-methyl-2-fluoropropane), 3-methyl-3-fluoropentane, 3-methyl-3-fluorohexane, 1-methyl-1-fluorocyclohexane, 1,3-difluoro-1,3,5-methylcyclooctane, 2-methyl-2-fluoroheptane, 1,2-difluoro-1-methylcyclooctane, 2-methyl-2-chloropropane, left-butyl chloride, 3-methyl-3-chloropentane, 3-chlorohexane, S-methyl-5-chlorohexane, 1-methyl-1-chlorocyclohexane, 1,3-dichloro-1,3,5-methylcyclooctane, 2-methyl-2-chloroheptane, 1,2-dichloro-1-methylcyclooctane, 2-methyl-2-bromoprop
- Suitable halohydrocarbons which have at least two different elements of halogen that may be used include, but are not limited to, 1-chloro-3-fluoro-1,3,5-methylcyclooctane, 2-bromo-1-fluoro-1-methylcyclooctane, 2-chloro-1-fluoro-1-methylcyclooctane, 1-(trichloromethyl)-4-(trifluoromethyl)benzene, 1-(dichloromethyl)-3-(dibromomethyl)benzene, 1-(bromomethyl)-2-(fluoromethyl)benzene, 1-(chloromethyl)-4-(trifluoromethyl)benzene, 1-(dichloromethyl)-3-(fluoromethyl)benzene, 1-(bromomethyl)-3,5-bis(trifluoromethyl)benzene, 1-(chloromethyl)-3,5-bis(trifluoromethyl)benzene, 1-(chloromethyl)-3,5-
- Suitable halohydrocarbons are tert-butyl fluoride, tert-butyl chloride, tert-butyl bromide, alpha,alpha,alpha-trifluorotoluene, 4-methyl-1-(trifluoromethyl)benzene, 3-methyl-1-(trifluoromethyl)benzene, triphenylfluoromethane, alpha,alpha,alpha-trichlorotoluene, 4-methyl-1-(trichloromethyl)benzene, 3-methyl-1-(trichloromethyl)benzene, triphenylchloromethane, alpha,alpha,alpha-tribromotoluene, 4-methyl-1-(tribromomethyl)benzene, 3-methyl-1-(tribromomethyl)benzene, and triphenylbromomethane.
- halohydrocarbons are alpha,alpha,alpha-trifluorotoluene, 4-methyl-1-(trifluoromethyl)benzene, alpha,alpha,alpha-trichlorotoluene, triphenylchloromethane, alpha,alpha,apha-tribromotoluene, and triphenylbromomethane.
- Additional suitable halohydrocarbons are alpha,alpha,alpha-trifluorotoluene, 4-methyl-1-(trifluoromethyl)benzene, triphenylchloromethane, and alpha,alpha,alpha-tribromotoluene.
- halogenation agent that can be used to form aluminoxane composition of this invention is at least one siloxane having at least one labile halogen atom in the molecule, wherein each halogen atom is, independently, fluorine, chlorine, or bromine.
- the halogenation agent can comprise Lewis base, e.g., at least one siloxane having at least one labile halogen atom is Lewis base.
- siloxanes have hydrocarbyl groups which can contain from about 1 to 30 carbon atoms and include linear and/or branched alkyl groups which contain from about 1 to 24 carbon atoms, cycloalkyl groups which contain from about 3 to 24 carbon atoms, and alkylaryl or aryl groups which contain from about 6 to 30 carbon atoms. At least one hydrocarbyl group of the siloxane contains at least one labile halogen atom.
- the siloxanes are chosen from disiloxanes and linear or cyclic polysiloxanes. The siloxanes contain the Si—O—Si bond and are substantially free of Si—OH bonds. The siloxanes can contain mixed hydrocarbyl groups.
- the polysiloxanes have a linear, or branched, or cyclic backbone of alternating silicon and oxygen atoms. If the polysiloxane is acyclic, it can be represented by the empirical formula, Si n O n ⁇ 1 , wherein n is at least 3 (or in the range of 3 to 8, or in the range of 3 to 4), and wherein the oxygen atoms are always individually disposed between and connected to two silicon atoms as a —Si—O—Si— moiety.
- the cyclic polysiloxanes can be represented by the empirical formula Si n O n where n is as defined above, and wherein, as in the case of the acyclic polysiloxanes, the oxygen atoms are always individually disposed between and connected to two silicon atoms as a —Si—O—Si-moiety.
- the backbone of a polysiloxane containing 4 or more silicon atoms can be branched on one or more of the silicon atoms of the backbone, in such case, the silicon atom that carries the branch is bonded to three or four separate oxygen atoms, and each such oxygen atom is in turn bonded to ah additional separate silicon atom.
- halosiloxanes include (trifluoromethyl)pentamethyldisiloxane, tris(fluoromethyl)trimethyldisiloxane, (2,2-difluoroethyl)pentaethyldisiloxane, bis(1,2-difluoroethyl)triethyldisiloxane, bis(trifluoromethyl)tetramethyldisiloxane, (trifluoromethyl)trimethyldicyclohexyldisiloxane, tetramethylbis(2,2-difluorocyclohexyl)disiloxane, tetramethylbutyl(4,4,4-trifluorobutyl)disiloxane, bis(p-trifluoromethylphenyl)tetraphenyldisiloxane, diphenyltrimethyl(difluoromethyl)disiloxane, tetraphenylbis(flufluoromethyl
- Suitable siloxanes having two or more different elements of halogen include, but are not limited to, (fluoromethyl)(chloromethyl)(bromomethyl)trimethyldisiloxane, (2,2-dichloroethyl)(2,2-difluoroethyl)tetraethyldisiloxane, (1,2-dichloroethyl)(1,2-difluoroethyl)triethyldisiloxane, (trichloromethyl)(tribromomethyl)tetramethyldisiloxane, tetramethyl(2,2-dichlorocyclohexyl)(fluoromethyl)disiloxane, tribromomethylphenyl)(p-trifluoromethylphenyl)(tetraphenyldisiloxane, tetraphenyl(chloromethyl)(fluoromethyl)disiloxane, (dichloromethyl)(d
- Suitable siloxanes are trisiloxanes and tricyclosiloxanes. Also suitable are siloxanes with at least one 3,3,3-trihalopropyl group. Additional suitable siloxanes include 3,3,3-trifluoropropylheptamethyltrisiloxane, 3,3,3-trifluoropropylheptamethylcyclotrisiloxane, tri[methyl(3,3,3-trifluoropropyl)cyclopolysiloxane], tetra[methyl(3,3,3-trifluoropropyl)cyclopolysiloxane], poly[methyl(3,3,3-trifluoropropyl)siloxane], poly[dimethylsiloxane-co-methyl(3,3,3-trifluoropropyl)siloxane]; 3,3,3-trichloropropylheptamethyltrisiloxane, 3,3,3-trichloropropylheptamethylcyclotrisiloxan
- 3,3,3-trifluoropropylheptamethyltrisiloxane 3,3,3-trifluoropropylheptamethylcyclotrisiloxane, poly[methyl(3,3,3-trifluoropropyl)siloxane], 3,3,3-trichloropropylheptamethyltrisiloxane, 3,3,3-trichloropropylheptamethylcyclotrisiloxane, poly[methyl(3,3,3-trichloropropyl)siloxane], 3,3,3-tribromopropylheptamethyltrisiloxane, 3,3,3-tribromopropylheptamethylcyolotrisiloxane, and poly[methyl(3,3,3-tribromopropyl)siloxane].
- siloxanes are poly[methyl(3,3,3-trifluoropropyl)siloxane], poly[methyl(3,3,3-trichloropropyl)siloxane], and poly[methyl(3,3,3-tribromopropyl)siloxane].
- R′ can be a straight chain, branched, cycloalkyl, aryl, or araalkyl group, R′ can be an aryl group; when R′ is an aryl group, it can have from six to about twenty carbon atoms; or it can be a phenyl group.
- R′ can be a straight chain or branched hydrocarbyl group, and when R′ is a straight chain or branched hydrocarbyl group, if can have from one to about twelve carbon atoms; or, R′ can have from one to about six carbon atoms; the straight chain or branched hydrocarbyl group can be a methyl group.
- Silanes that can be used as halogenation agents include, but are not limited to, trimethylfluorosilane, dimethyldifluorosilane, diethyldifluorosilane, diisopropyldifluorosilane, tert-butyltrifluorosilane, dicyclobutyldifluorosilane, tripentylfluorosilane, dicyclohexyldifluorosilane, triheptylfluorosilane, dicyclooctyldifluorosilane, triphenylfluorosilane, diphenyldifluorosilane, phenyltrifluorosilane, phenyldimethylfluorosilane, diphenylmethylfluorosilane, phenylmethyldifluorosilane, phenyldiisopropylfluorosilane, tritolylfluorosilane, ditolyldifluorosilane,
- R′ can be a straight chain, branched, cycloalkyl, aryl, or araalkyl group.
- R′ can be an aryl group, or, a straight chain or branched hydrocarbyl group.
- R′ When R′ is an aryl group, it can have from six to about twenty carbon atoms; the aryl group can be a phenyl group.
- R′ When R′ is a straight chain or branched hydrocarbyl group, it can have from one to about twelve carbon atoms; R′ can have from one to about six carbon atoms; a suitable straight chain or branched hydrocarbyl group is a methyl group.
- Tin compounds that can be used as halogenation agents include trimethylfluorostannane, diethylfluorostannane, di-n-propyldifluorostannane, tri-n-butylfluorostannane, dipentyldifluorostannane, cyclohexyltrifluorostannane, diheptyldifluorostannane, trioctylfluorostannane, didodecyldifluorostannane, dichlorodimethylstannane, trichloromethylstannane, triethylchlorostannane, diisopropyldichlorostannane, dicyclobutyldichlorostannane, cyclopentyltrichlorostannane, trihexylchlorostannane, dicycloheptyldichlorostannane, octyltrichlorostannane, dinonyld
- R′′ can be a straight chain, branched, cycloalkyl, aryl, or araalkyl group.
- R′′ can be a straight chain; the straight chain can have from one to about fen carbon atoms.
- Hydrocarbyl aluminum halides that can be used as halogenation agents include, but are not limited to, methylaluminum difluoride, dimethylaluminum fluoride, ethylaluminum difluoride, diethylaluminum fluoride, isopropylaluminum difluoride, diisopropylaluminum fluoride, n-butylaluminum difluoride, isobutylaluminum difluoride, diisobutylaluminum fluoride, dipentylaluminum fluoride, cyclohexylaluminum difluoride, diheptylaluminum fluoride, dicyclooctylaluminum fluoride, nonylaluminum difluoride, decylaluminum difluoride, diundecylaluminum fluoride, phenylaluminum difluoride, diphenylaluminum fluoride, tolylalumin
- Suitable hydrocarbyl aluminum halides are methylaluminum difluoride, dimethylaluminum fluoride, methylaluminum dichloride, dimethylaluminum chloride, methylaluminum dibromide, and dimethylaluminum bromide. Also suitable are methylaluminum difluoride and dimethylaluminum fluoride.
- mixtures of two or more halogenation agents may be used. This includes mixtures of different halogenation agents within the same type, mixtures of halogenation agents of different types, and mixtures of at least two different halogenation agents within the same type with at least one halogenation agent of a different type. Mixtures may be used in which the halogen elements in the halogenation agents are the same or different. It may be advantageous to use a mixture of halogenation agents, depending on the desired product aluminoxane source and the properties thereof (e.g., degree of halogenation, solubility, and stability).
- Lewis base (C) can comprise mono-dentate donor such as NR 2 3 , (wherein each R 2 is independently hydrogen or hydrocarbyl group having up to about 24 carbon atoms, or multi-dentate donor such as octamethyltrisiloxane (OMTS, Me 3 SiOSi(Me) 2 OSiMe 3 ).
- mono-dentate donor such as NR 2 3 , (wherein each R 2 is independently hydrogen or hydrocarbyl group having up to about 24 carbon atoms, or multi-dentate donor such as octamethyltrisiloxane (OMTS, Me 3 SiOSi(Me) 2 OSiMe 3 ).
- Lewis bases can be used in this invention, including (i) those with O donor, such as mono-dentate ethers (e.g., R 2 2 O, tetrahydrofuran (THF), R 2 3 SiOSiR 2 3 ) and multi-dentate ethers (e.g., OMTS, EtOCH 2 CH 2 OEt), (II) those with N donor, such as mono-dentate amines (e.g., NR 2 3 , C 5 H 5 N, C 4 H 4 N, (R 2 3 Si) 3 M) and multi-dentate amines (e.g., Et 2 NCH 2 CH 2 NEt 2 ), and (iii) those with P or S mono-dentate and multi-dentate donors (e.g., NR 2 3 , PR 2 3 , and SR 2 2 ), and the like.
- O donor such as mono-dentate ethers (e.g., R 2 2 O, tetrahydrofuran (THF), R 2
- Lewis base (C) can comprise oxygen donors such as siloxanes, ethers or amine donors such as primary amine NH 2 R 2 , secondary amine NHR 2 2 , or tertiary amine NR 2 3 , or any mixture thereof, wherein R 2 in each occurrence is selected independently from hydrocarbyl group having up to about 20 carbon atoms, or hydrogen; and for amines having more than one R 2 , each R 2 can be the same as or different from any other R 2 .
- oxygen donors such as siloxanes, ethers or amine donors such as primary amine NH 2 R 2 , secondary amine NHR 2 2 , or tertiary amine NR 2 3 , or any mixture thereof, wherein R 2 in each occurrence is selected independently from hydrocarbyl group having up to about 20 carbon atoms, or hydrogen; and for amines having more than one R 2 , each R 2 can be the same as or different from any other R 2 .
- Lewis base (C) can comprise a variety of amines, Including, but not limited to, NMe 2 Ph, NMe 2 (CH 2 Ph), NEt 2 Ph, NEt 2 (CH 2 Ph), or Lewis base (C) can comprise one or more long chain amines such as NMe(C n H 2n+1 )(C m H 2m+1 ), NMe 2 (C n H 2n+1 ), NEt(C n H 2n+1 )(C m H 2m+1 ), or NEt 2 (C n H 2n+1 ), wherein n and m are selected independently from an integer from about 3 to about 20.
- Examples of long chain amines of the formula NMe(C n H 2n+1 )(C m H 2m+1 ) include, but are not limited to, compounds such as NMe(C 16 H 33 ) 2 , NMe(C 17 H 35 ) 2 , NMe(C 18 H 37 ) 2 , NMe(C 15 H 33 )(C 17 H 35 ), NMe(C 16 H 33 )(C 18 H 37 ), NMe(C 17 H 35 )(C 18 H 37 ), and the like.
- NMe(C 18 H 33 ) 2 is typically the major species in a commercial long chain amine composition that usually comprises a mixture of several amines
- Lewis base (C) can comprise NMe 2 Ph, NMe 2 (CH 2 Ph), NEt 2 Ph, NEt 2 (CH 2 Ph), NMe(C 16 H 33 ) 2 .
- Lewis base (C) can also comprise phosphines.
- Lewis base (C) can comprise at least one siloxane having at least one labile halogen atom, for example, poly[methyl(3,3,3-trifluoropropyl)siloxane].
- Non-limiting examples include: C 6 H 5 F (fluorobenzene), C 6 H 5 Cl (chlorobenzene), Et 2 O (diethylether), t BuOMe (t-butylmethylether), i Pr 2 O (diisopropylether), (SiMe 3 ) 2 O (hexamethyldisilosane), C 4 H 8 O (tetrahydrofuran), PhNMe 2 (dimethylaniline), Et 3 N (triethylamine), PhCH 2 NMe 2 (dimethylbenzoamine), C 5 H 5 N (pyridine), and (CH 2 ) 5 NMe (N-methylpiperidine).
- Lewis base (C) can comprise bidentate Lewis base
- Non-limiting examples include: 1,2-F 2 C 6 H 4 (1,2-difluorobenzene), 1,2-Cl 2 C 6 H 4 (1,2-dichlorobenzene), EtOCH 2 CH 2 OEt (ethyleneglycoldiethylether), (Me 3 SiO) 2 SiMe 2 (OMTS, octamethyltrisiloxane), Me 2 N(CH 2 CH 2 )NMe 2 (TMEDA, N,N′,N′-tetramethylethylenediamine), and Et 2 N(CH 2 CH 2 )NEt 2 (N,N,N′,N′-tetramethylenediamine).
- Lewis base (C) can comprise NMeR 4 2 , where R 4 is C16-18 long chain alkyl).
- Transition metal component (DJ can comprise any transition metal component having olefin polymerization potential.
- transition metal component (D) can comprise one or more metallocene transition metal components.
- metallocene transition metal components for example, without limiting this invention, halogen, alkoxy, aryloxy, amide, or hydrocarbyl transition metal components are ail suitable.
- Transition metal component (D) can comprise catalyst precursor ML a X n ⁇ a ;
- M represents any transition metal catalyst compound in which the transition metal thereof is Group 3 to 10 of the Periodic Table including compounds of metal of lanthanide or actinide series.
- the Periodic Table referred to herein is that appearing on page 27 of the Feb. 4, 1985 issue of Chemical & Engineering News .
- Suitable catalyst compounds can also be described as d- and f-block metal compounds. See, for example, the Periodic Table appearing on page 225 of Moeller, et al., Chemistry , Second Edition, Academic Press, copyright 1984.
- Metal constituent of M may comprise Fe, Co, Ni, Pd, and V, and may comprise metals of Groups 4-6 (Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W.
- transition metal catalyst compounds used in this Invention can be one or more of any Ziegler-Natta catalyst compound, any metallocene, any single-site non-metallocene, any compound of constrained geometry, any late transition metal complex, and any other transition metal compound or complex reported in the literature or otherwise generally known in the art to be an effective catalyst compound when suitably activated, including mixtures of at least two different types of such transition metal compounds or complexes, such as for example a mixture of a metallocene and a Ziegler-Natta olefin polymerization catalyst compound.
- L represents group having ligand suitable for either Ziegler-Natta type catalyst precursor, or metallocene type catalyst precursor, or non-metallocene single-site catalyst precursor. At least one L may be group having cyclopentadienyl skeleton, or may be non-cyclopentdienyl; and a plurality of L may be the same or different and may be crosslinked to each other;
- X represents halogen, alkoxy, aryloxy, amide or hydrocarbyl group having 1 to about 20 carbon atoms; “a” represents a numeral satisfying the expression 0 ⁇ a ⁇ n; and n represents valence of transition metal atom M).
- group having cyclopentadienyl skeleton can comprise, for example, cyclopentadienyl group, substituted cyclopentadienyl group or polycyclic group having cyclopentadienyl skeleton.
- Example substituted cyclopentadienyl groups include hydrocarbon group having 1 to about 20 carbon atoms, halogenated hydrocarbon group having 1 to about 20 carbon atoms, silyl group having 1 to about 20 carbon atoms and the like, Silyl group according to this invention can include SiMe 3 and the like.
- Examples of polycyclic group having cyclopentadienyl skeleton include indenyl group, fluorenyl group and the like.
- Examples of hetero atom; of the group having at least one hetero atom include nitrogen atom, oxygen atom, phosphorous atom, sulfur atom and the like.
- Example non-metallocene d-block or f-block metal compounds that can be used in this invention include, but are not limited to, transition metal compounds suitable for olefin polymerization such as Ziegler-Natta type catalysts.
- transition metal of Ziegler-Natta catalysts comprises at least two hydrocarbyl ligands. Examples of Ziegler-Natta catalyst systems are disclosed in U.S. Patent Application Number 2004/0102312, and are described herein as follows.
- Representative traditional Ziegler-Natta transition metal compounds include, but are not limited to, tetrabenzyl zirconium, tetrakis(trimethylsilylmethyl)zirconium, oxotris(trimethylsilylmethyl)vanadium, tetrabenzyl hafnium, tetrabenzyl titanium, bis(hexamethyl disilazido)dimethyl titanium, tris(trimethylsilylmethyl)niobium dichloride, tris(trimethylsilylmethyl)tantalum dichloride, and combinations thereof.
- Ziegler-Natta type systems that can be used in this invention include, but are not limited to, transition metal halides, oxyhalides or alkoxyhalides in the presence of an alkylating agent such as a dialkylaluminum alkoxide or trialkyl aluminum compound.
- Examples of this Ziegler-Natta type system include, but are not limited to, titanium and vanadium halides, oxyhalides or alkoxyhalides, such as titanium tetrachloride (TiCl 4 ), vanadium tetrachloride (VCl 4 ) and vanadium oxytrichloride (VOCl 3 ), and titanium and vanadium alkoxides, wherein the alkoxide moiety has a branched or unbranched alkyl group from 1 to 20 carbon atoms, or from 1 to 8 carbon atoms.
- TiCl 4 titanium tetrachloride
- VCl 4 vanadium tetrachloride
- VOCl 3 vanadium oxytrichloride
- titanium and vanadium alkoxides wherein the alkoxide moiety has a branched or unbranched alkyl group from 1 to 20 carbon atoms, or from 1 to 8 carbon atoms.
- useful d-block or f-block metal compounds that can be used in this invention include, but are not limited to, the Group 15-containing compounds, such as those disclosed in U.S. Patent Application Number 2004/0162312, and defined above,
- Group 15-containing compounds include, but are not limited to, Group 4 imino-phenol complexes, Group 4 bis(amido) complexes, and Group 4 pyridyl-amide complexes that are active towards olefin polymerization to any extent.
- the Group 15-containing catalyst component can be described by the following formula: ⁇ b ( ⁇ ) a ⁇ g MX n ; wherein: ⁇ and ⁇ are groups that each comprise at least one Group 14 to Group 16 atom; and ⁇ (when present) and ⁇ are groups bonded to M through from 1 to 4 Group 14 to Group 16 atoms, wherein at least two atoms are Group 15-containing atoms; more particularly: ⁇ and ⁇ are groups selected from Group 14 and Group 15-containing (and their non-valent equivalents when not linked by a group ⁇ ): alkyls, aryls, alkylaryls, and heterocyclic hydrocarbons, and chemically bonded combinations thereof.
- chemically bonded combinations thereof means that adjacent groups, ( ⁇ and ⁇ groups) can form a chemical bond between them; in one aspect, the ⁇ and ⁇ groups are chemically bonded through one or more a groups there between.
- alkyleneamines As used herein, the terms “alkyleneamines”, “aryleneamines”, describe alkylamines and arylamines (respectively) that are deficient by two hydrogens, thus capable of forming chemical bonds with two adjacent ⁇ groups, or adjacent ⁇ and ⁇ groups.
- examples of an alkyleneamine include, but are not limited to, —CH 2 CH 2 N(CH 3 )CH 2 CH 2 — and —CH 2 CH 2 N(H)CH 2 CH 2 —.
- heterocyclic hydrocarbylene or aryleneamine include, but are not limited to, —C 5 H 3 N— (divalent pyridine).
- An “alkylene-arylamine” includes a group such as, for example, —CH 2 CH 2 (C 5 H 3 N)CH 2 CH 2 —.
- Examples of compounds having the general formula ⁇ b ( ⁇ ) a ⁇ g MX n include, but are not limited to, the following compounds:
- examples of Ar include 2-MeC 6 H 4 , 2,4,6-Me 3 C 6 H 2 , 2-i-PrC 6 H 4 , and the like; and examples of M include Fe or Ni; and examples of X include Cl, Br, or a C 1 to C 12 hydrocarbyl;
- examples of R 2 and R 5 include 2,6-i-Pr 2 C 6 H 3 , 2,6-Me 2 C 6 H 3 , and 2,4,6-Me 3 C 6 H 2 ;
- examples of R 3 and R 4 include methyl, ethyl, propyl, butyl, and benzyl;
- examples of M include Pd and Ni;
- examples of X include Cl, Br, and a C 1 to C 12 hydrocarbyl such as Me;
- examples of Ar 1 include 2,6-Me 2 C 6 H 3 , and 2,6i-Pr 2 C 6 H 3
- examples of Ar 2 include 2,6-Me 2 C 6 H 3 , 2,4,6-Me 3 C 6 H 2 , 2,6-i-Pr 2 C 6 H 3 , and 2,8-Pr 2 C 6 H 3
- examples of M include V
- examples of X include Cl, Br, and a C 1 to Cl 12 hydrocarbyl
- examples of M include Zr or Hf
- examples of X include a C 1 to C 12 hydrocarbyl such as CH 2 C 6 H 5
- examples of R include Me, Ph, or t-Bu
- examples of 0 include NMe 2 , OMe, and the like; and 5. Any Combination of the Above Compounds.
- these metal compounds typically are used in conjunction with an alkylating agent such as a trialkyl aluminum or alkoxyaluminum dialkyl reagent to convert these compounds to the corresponding dialkyl species.
- an alkylating agent such as a trialkyl aluminum or alkoxyaluminum dialkyl reagent to convert these compounds to the corresponding dialkyl species.
- Example substituted cyclopentadienyl groups include methylcyclopentadienyl group, ethylcyclopentadienyl group, n-propylcyclopentadienyl group, n-butylcyclopentadienyl group, isopropylcyclopentadienyl group, isobutylcyclopentadienyl group, sec-butylcyclopentadienyl group, tertbutylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,2,3-trimethylcyclopentadienyl group, 1,2,4-trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group and the like.
- Example polycyclic groups having cyclopentadienyl group include indenyl group, 4,5,6,7-tetrahydroindenyl group, fluorenyl group and the like.
- Example groups having at least one hetero atom include methylamino group, tert-butylamino group, benzylamino group, methoxy group, tert-butoxy group, phenoxy group, pyrrolyl group, thiomethoxy group and the like.
- One or more groups having cyclopentadienyl skeleton, or one or more group having cyclopentadienyl skeleton and one or more group having at least one hetero atom may be crosslinked with (i) alkylene group such as ethylene, propylene and the like; (ii) substituted alkylene group such as isopropylidene, diphenylmethylene and the like; or (iii) silylene group or substituted silylene group such as dimethylsilylene group, diphenylsilylene group, methylsilylsilylene group and the like.
- transition metal component (D) ML a X n ⁇ a wherein M comprises zirconium
- examples of transition metal component (D) ML a X n ⁇ a , wherein M comprises zirconium include bis(cyclopentadienyl)zirconiumdichloride, bis(methylcyclopentadienyl)zirconiumdichloride, bis(pentamethylcyclopentadienyl)zirconiumdichloride, bis(indenyl)zirconiumdichloride, bis(4,5,6,7-tetrahydroindenyl) zirconiumdichloride, bis(fluorenyl)zirconiumdichloride, ethylenebis(indenyl)zirconiumdichloride, dimethylsilylene(cyclopentadienylfluorenyl)zirconiumdichloride, diphenylsilylenebis(indenyl) zirconiumdichloride, cyclopenta
- Additional exemplary transition metal component (D) ML a X n ⁇ a include components wherein zirconium is replaced with titanium or hafnium in the above zirconium components.
- Alkylated catalyst precursors useful in this invention are; rac-dimethylsilylbis(2-methyl-4-phenyl-indenyl)zirconium dimethyl; rac-dimethylsilylbis(2-methyl-1-indenyl) zirconium dimethyl; rac-dimethylsilylbis(2-methyl-4,5-benzoindenyl) zirconium dimethyl; ethylenebis(tetrahydroindenyl)zirconium dimethyl, and ethylenebis(indenyl)zirconium dimethyl.
- Alkylated catalyst precursor can be generated in-situ through reaction of alkylation agent with the halogenated version of the catalyst precursor. For example, bis(cyclopentadienyl)zirconium dimethyl can be treated with triisobutylaluminum (TIBA) and then combined with activator composition (E).
- TIBA triisobutylaluminum
- Additional non-limiting and representative metallocene compounds that can be used in the present invention include mono-cyclopentadienyl compounds such as pentamethylcyclopentadienyl titanium trimethyl, pentamethylcyclopentadienyl titanium tribenzyl, dimethylsilyltetramethyl-cyclopentadienyl-tert-butylamido titanium dimethyl, dimethylsilyltetramethylcyclopentadienyl-tert-butylamido zirconium dimethyl, dimethylsilyltetramethylcyclopentadienyl-dodecylamido hafnium dihydride, dimethylsliyitetramethylcyclopentadienyl-dodecylamido hafnium dimethyl, unbridged biscyclopentadienyl compounds such as bis(1,3-butylmethylcyclopentadienyl)zirconium dimethyl, bis(1,3-butylmethylcyclopentadien
- Activator composition (E) comprises aluminoxane source (A), halogen source (B), and Lewis base (C).
- Activator composition (E) can be derived from aluminoxane source (A), halogen source (B), and Lewis base (C) combined in any order.
- Activator composition (E) can be obtained by combining aluminoxane source (A) with Lewis base (C), followed by combining with halogen source (B). In this application, unless an order of combination is stated, no specific order of combination is intended or implied.
- Activator composition (E) can be derived from a method whereby aluminoxane source (A) is combined with Lewis base (C) comprising NR 2 3 , wherein each R 2 is independently hydrogen atom or hydrocarbyl group having up to about 24 carbon atoms to form first product and at least a portion of the first product is combined with halogen source (B) comprising alpha, alpha, alpha-trifluorotoluene.
- Activator composition (E) and transition metal component (D) can be each added independently, yet substantially simultaneously, to monomer to catalyze polymerization. Activator composition (E) and transition metal component (D) can be combined to form product and at least a portion of product can be added to monomer to catalyze polymerization.
- the ratio of activator composition (E) to transition metal atom (M) of transition metal component (D) based on M to Al atom can be 1 to 10,000, or 10 to 1000, or 30 to 500.
- any olefin or dioelfin having 2 to 20 carbon atoms can be used as a monomer for polymerization.
- Specific examples thereof include ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, hexadecane-1, eicocene-1,4-methylpentene-1,5-methyl-2-pentene-1, vinylcyclohexane, styrene, dicyclopentadiene, norbornene, 5-ethylidene-2-norbornene and the like, but are not limited thereto.
- copolymerization can be conducted using two or more monomers, simultaneously.
- the monomers constituting the copolymer include ethylene/an ⁇ olefin such as ethylene/propylene, ethylene/butene-1, ethylene/hexene-1, ethylene/propylene/butene-1, ethylene/propylene/5-ethylidene-2-norbornene and the like, propylene/butene-1, and the like, but are not limited thereto.
- the polymerization temperature can be from about ⁇ 50° C. to about 200° C., or from 0° C. to about 100° C.
- the polymerization pressure can be from atmospheric pressure to about 100 kg/cm 2 , or from atmospheric pressure to about 50 kg/cm 2 .
- Appropriate polymerization time can be determined by means known to those skilled in the art according to the desired olefin polymer and reaction apparatus, and is typically within the range from about 1 minute to about 20 hours.
- a chain transfer agent such as hydrogen may be added to adjust the molecular weight of olefin polymer to be obtained in polymerization.
- Organoaluminum compound can be added during polymerization to remove Impurities, such as water.
- Organoaluminum compound useful herein can comprise a variety of organoaluminum compounds, including at least one currently known organoaluminum compound, for example, organoaluminum compound R 3 c AlY 3 ⁇ c (wherein R 3 represents hydrocarbon group having 1 to about 20 carbon atoms; Y represents hydrogen atom and/or halogen atoms; and “c” represents an integer of 0 to 3).
- organoaluminum compound R 3 c AlY 3 ⁇ c wherein R 3 represents hydrocarbon group having 1 to about 20 carbon atoms; Y represents hydrogen atom and/or halogen atoms; and “c” represents an integer of 0 to 3).
- R 3 include methyl group, ethyl group, n-propyl group, n-butyl group, isobutyl group, n-hexyl group and the like.
- halogen atom for Y include fluorine atom, chlorine atom, bromine atom and iodine atom.
- organoaluminum compound R 3 c AlY 3 ⁇ c include trialkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, trisobutylaluminum, tri-n-hexylaluminum and the like; dialkylaluminum chloride such as dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, diisobutylaluminum chloride, di-n-hexylaluminum chloride and the like; alkylaluminum dichlorides such as methylaluminumdichloride, ethylaluminum dichloride, n-propylaluminum dichloride, isobutylaluminum dichloride, n-hexyla
- the sample was tested for ethylene polymerization using standard procedures (described In Example 6). Then the sample was sealed with electrical tapes, taken out of the drybox, and placed in a 45° C. oil-bath for 2 months. The sample was still clear, no indication of typical MAO gel formation. The sample was then discarded after heating.
- the gel formation data and polymerization test results are listed in Table 1 column and Table 2 column 7, respectively.
- the sample was tested for ethylene polymerization using standard polymerization procedures (described in Example 6). Then the sample was aged for 6 months at ambient indoor (about 20-25° C. range) and analyzed for gel content. After 18 months of aging at ambient, the sample was tested for ethylene polymerization again and re-analyzed for gel content.
- the gel formation data and polymerization test results are listed in Table 1 Column 8 and Table 2 Column 8, respectively.
- Preparation of Active Catalyst Solution A 5 mL dried syringe was tared without the needle on the balance in the dry box. A desired amount of activator solution was weighed into the syringe based on Al:Zr 400:1 or 50:1 3, Add 1.00 g (0.5 g for OMTS modified F-MAO activators) zirconocene solution into the syringe with the activator sample. Attach a 12 inch 18 gauge needle to the syringe, cap the needle with a crimp-top vial, and note the time that the pre-contact solution was completed.
- Run time was 15 or 30 minutes; temperature, pressure, and agitator speed were controlled at 70° C., 50 psi, and 800-825 rpm, respectively.
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Abstract
Description
ArGn
where Ar is an aromatic hydrocarbon ring system, which typically contains up to about 25 carbon atoms, or up to about 12 carbon atoms, or 6 carbon atoms in the ring system (i.e., excluding X and excluding any substituents that may be present on the ring(s)); G is —CX3, —CX2R, or —CXR2, in which X is, independently, a fluorine atom, chlorine atom, or bromine atom, and in which R is, independently, a hydrogen atom or C-m alkyl group; and n is 1 to 5, or 1 to 3, or 1 or 2, G can be a trihalomethyl group.
(where X=halogen, n=0; where X═O or S, n=1; where X═N or P, n= 2; and brdg=organic bridge biradical fragment, e.g., —CH2CH2— or —SiMe2—). Non-limiting examples include:
1,2-F2C6H4 (1,2-difluorobenzene), 1,2-Cl2C6H4 (1,2-dichlorobenzene), EtOCH2CH2OEt (ethyleneglycoldiethylether), (Me3SiO)2SiMe2 (OMTS, octamethyltrisiloxane), Me2N(CH2CH2)NMe2 (TMEDA, N,N′,N′-tetramethylethylenediamine), and Et2N(CH2CH2)NEt2 (N,N,N′,N′-tetramethylenediamine).
βb(α)aγgMXn; wherein:
β and γ are groups that each comprise at least one Group 14 to Group 16 atom; and β (when present) and γ are groups bonded to M through from 1 to 4 Group 14 to Group 16 atoms, wherein at least two atoms are Group 15-containing atoms; more particularly: β and γ are groups selected from Group 14 and Group 15-containing (and their non-valent equivalents when not linked by a group α): alkyls, aryls, alkylaryls, and heterocyclic hydrocarbons, and chemically bonded combinations thereof. In one aspect; and selected from Group 14 and Group 15-containing: C1 to C10 alkyls, C6 to C12aryls, C6 to C18 alkylaryls, and C4 to C12 heterocyclic hydrocarbons, and chemically bonded combinations thereof in a further aspect; and selected from C1 to C10 alkylamines, C1 to C10 alkoxys, C6 to C20 alkylarylamines, C6 to C18 alkylaryloxys, and C4 to C12 nitrogen containing heterocyclic hydrocarbons, and C4 to C12 alkyl substituted nitrogen containing heterocyclic hydrocarbons and chemically bonded combinations thereof in still another aspect; and selected from anilinyls, pyridyls, quinolyls, pyrrolyls, pyrimidyls, purinyls, imidazyls, indolyls, C1 to C6 alkyl substituted groups selected from anilinyls, pyridyls, quinolyls, pyrrolyls, pyrimidyls, purinyls, imidazyls, indolyls; C1 to C6 alkylamine substituted groups selected from anilinyls, pyridyls, quinolyls, pyrrolyls, pyrimidyls, purinyls, imidazyls, indolyls, amine substituted anilinyls, pyridyls, quinolyls, pyrrolyls, pyrimidyls, purinyls, imidazyls, and indolyls; hydroxy substituted groups selected from anilinyls, pyridyls, quinolyls, pyrrolyls, pyrimidyls, purinyls, imidazyls, and indolyls; methyl-substituted phenylamines, and chemically bonded combinations thereof in yet a further aspect:
α can be a linking (or “bridging”) moiety that, when present, forms a chemical bond to each of β and γ, or to two γ moieties, thus forming a “γαγ” “γαβ” ligand bound to M; α can also include a Group 14 to Group 16 atom which can be bonded to M through the Group 14 to Group 18 atom in one aspect; and more particularly, α can be a divalent bridging group selected from alkylenes, arylenes, alkenylenes, heterocyclic arylenes, alkylarylenes, heteroatom containing alkylenes, heteroatom containing alkenylenes and heterocyclic hydrocarbonylenes in another aspect; and selected from C1 to C10 alkylenes, C2 to C10 alkenylenes, C6 to C12 arylenes, C1 to C10 divalent ethers, C6 to C12O- or N-containing arylenes, C2 to C10 alkyleneamines, C6 to C12 aryleneamines, and substituted derivatives thereof in yet a further aspect;
-
- a is typically 0 or 1;
- b is typically an integer from 0 to 2;
- g is an integer from 1 to 2; wherein in one aspect, a is 1, b is 0, and g is 2;
- M is selected from Group 3 to Group 12 atoms in one aspect; and selected from Group 3 to Group 10 atoms in a further aspect; and selected from Group 3 to Group 6 atoms in yet another aspect; and selected from Ni, Cr, Ti, Zr and Hf in still a further aspect; and selected from Zr and Hf in yet one other aspect;
- each X is as defined above for A and B in structure (V); and
- n is an integer from 0 to 4 in one: aspect; and an integer from 1 to 3 in another aspect; and an integer from 2 to 3 in still another aspect.
including compounds such as those disclosed in WO 99/02472, wherein examples of Ar include 2-MeC6H4, 2,4,6-Me3C6H2, 2-i-PrC6H4, and the like; and examples of M include Fe or Ni; and examples of X include Cl, Br, or a C1 to C12 hydrocarbyl;
including compounds such as those disclosed in U.S. Pat. No. 5,880,241, wherein examples of R2 and R5 (as used therein) include 2,6-i-Pr2C6H3, 2,6-Me2C6H3, and 2,4,6-Me3C6H2; examples of R3 and R4 (as used therein) include methyl, ethyl, propyl, butyl, and benzyl; examples of M include Pd and Ni; and examples of X include Cl, Br, and a C1 to C12 hydrocarbyl such as Me;
including compounds such as those disclosed in Nomura et al., Macromolecules, 2005, in press (Abstract published by the American Chemical Society, Macromolecules, ASAP Article 10.1021/ma059629s; 80024-9297(05)00829-7; Web Release Date Jun. 15, 2005), wherein examples of Ar1 include 2,6-Me2C6H3, and 2,6i-Pr2C6H3; examples of Ar2 include 2,6-Me2C6H3, 2,4,6-Me3C6H2, 2,6-i-Pr2C6H3, and 2,8-Pr2C6H3; examples of M include V; and examples of X include Cl, Br, and a C1 to Cl12 hydrocarbyl;
including compounds such as those disclosed in Weymouth et al., Macromolecules, 2005, 38, 2552-2558, wherein examples of M include Zr or Hf; examples of X include a C1 to C12 hydrocarbyl such as CH2C6H5; examples of R (as used therein) include Me, Ph, or t-Bu; and examples of 0 include NMe2, OMe, and the like; and
5. Any Combination of the Above Compounds.
TABLE 1 |
Gel Data for Lewis Base Modified, Partially Halogenated |
Aluminoxane Compositions of This Invention |
OMTS | OMTS | OMTS | Amine | Amine and | |||
treated | treated | treated | treated | TFT-treated | |||
F-MAO | F-MAO | F-MAO | F-MAO | MAO | |||
MAO | F-MAO4 | EX. 2 | EX. 1 | EX. 3 | EX. 4 | EX. 5 | |
col. 1 | col. 2 | col. 3 | col. 4 | col. 5 | col. 6 | col. 7 | col. 8 |
OMTS | 0 | 0 | 0.9 | 2.0 | 8 | 0 | 0 |
(mol % relative | |||||||
to Al atoms) | |||||||
NR3 1 | 0 | 0 | 0 | 0 | 0 | 6 | 10 |
(mol % relative | |||||||
to Al atoms) | |||||||
F | 0 | 4.3 | 3.6 | 4.3 | 4.3 | 4.5 | 5.0 |
(mol % relative | |||||||
to Al atoms) | |||||||
Gel (%) | Solidified | 6 | 0 | 0 | 0 | 03 | 0 |
after 6 months | |||||||
Gel (%) | — | — | 0 (16.2)2 | 0 | 0 (32.0)2 | — | 0 |
after 18 months | |||||||
1NR3 is a long chain amine NMeR2 with R = alkyl containing 16 to 18 carbons. | |||||||
2No solid MAO gel formed. However, a sticky liquid phase under the bottom of the container formed. The number in the bracket indicates the amount of the second layer liquid in wt %. | |||||||
3Heated at 45° C. for 2 months. | |||||||
4Partially flourinated MAO. |
TABLE 2 |
Polyethylene (PE) Productivity for Ethylenebis(indenyl) Zirconium |
Dimethyl Activated with Methylaluminoxane, with Partially Halo- |
genated Methylaluminoxane, and with Compositions of This Invention |
OMTS | OMTS | OMTS | Amine | Amine and | |||
treated | treated | treated | treated | TFT treated | |||
F-MAO | F-MAO | F-MAO | F-MAO | MAO | |||
MAO | F-MAO3 | EX. 2 | EX. 1 | EX. 3 | EX. 4 | EX. 5 | |
col. 1 | col. 2 | col. 3 | Col. 4 | col. 5 | col. 6 | col. 7 | col. 8 |
OMTS | 0 | 0 | 1 | 2 | 8 | 0 | 0 |
(mol % relative | |||||||
to Al atoms) | |||||||
NR3 | 0 | 0 | 0 | 0 | 0 | 6 | 10 |
(mol % relative | |||||||
to Al atoms) | |||||||
F | 0 | 4.3 | 3.6 | 4.3 | 4.3 | 4.5 | 5.0 |
(mol % relative | |||||||
to Al atoms) | |||||||
Activity | 28/41 | 60/86 | — | 272/293 | — | 130 | 44 |
(kg/mmol Zr/hr) | |||||||
for Al:Zr = 50:1 | |||||||
(fresh) | |||||||
Activity | 112/130 | 145/182 | — | too hot1 | — | 134 | 59 |
(kg/mmol Zr/hr) | |||||||
for Al:Zr = 400:1 | |||||||
(fresh) | |||||||
Activity | — | — | 274 | 246/268 | 354 too | — | 38 |
(kg/mmol Zr/hr) | hot1 | ||||||
for Al:Zr = 50:1 | |||||||
(18 months)2 | |||||||
(2 L autoclave, 70° C., 50 PSI, 2.15 μmol ethylenebis(indenyl)zirconium dimethyl (1.08 μmol for composition of this invention), 1 ml of 10% TIBA in hexane, 15 min) | |||||||
1Reaction temperature not controllable with cooling system, due to speed of polymerization being too fast for obtaining an accurate activity result. | |||||||
2Aged at room temperature for 18 months. | |||||||
3Partially fluorinated MAO. |
Claims (19)
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US (1) | US7960488B2 (en) |
EP (1) | EP2013246B1 (en) |
JP (1) | JP5775259B2 (en) |
KR (1) | KR101461241B1 (en) |
CN (1) | CN101437858B (en) |
CA (1) | CA2650483C (en) |
ES (1) | ES2766851T3 (en) |
HU (1) | HUE048053T2 (en) |
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Cited By (5)
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WO2016196334A1 (en) | 2015-06-05 | 2016-12-08 | Exxonmobil Chemical Patents Inc. | Single reactor production of polymers in gas or slurry phase |
WO2016197037A1 (en) | 2015-06-05 | 2016-12-08 | Exxonmobil Chemical Patents Inc. | Catalyst system comprising supported alumoxane and unsupported alumoxane particles |
WO2016196339A2 (en) | 2015-06-05 | 2016-12-08 | Exxonmobil Chemical Patents Inc. | Production of heterophasic polymers in gas or slurry phase |
WO2021247244A2 (en) | 2020-06-03 | 2021-12-09 | Exxonmobil Chemical Patents Inc. | Process for production of thermoplastic vulcanizates using supported catalyst systems and compositions made therefrom |
US11485815B2 (en) | 2018-04-11 | 2022-11-01 | Mitsui Chemicals, Inc. | 4-methyl-1-pentene polymer particle and method for producing 4-methyl-1-pentene resin |
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WO2009046144A1 (en) * | 2007-10-01 | 2009-04-09 | California Institute Of Technology | Solvent, additive and co-catalyst effects for ethylene oligomerization catalysis |
EP2386583A1 (en) | 2010-05-07 | 2011-11-16 | Borealis AG | Process for the preparation of a solid metallocene catalyst system and its use in polymerisation of olefins |
SG189518A1 (en) | 2010-11-22 | 2013-05-31 | Albemarle Corp | Activator compositions, their preparation, and their use in catalysis |
TWI555574B (en) * | 2011-03-09 | 2016-11-01 | 亞比馬利股份有限公司 | Aluminoxane catalyst activators containing carbocation agents, and use thereof in polyolefin catalysts |
KR102064629B1 (en) | 2012-04-27 | 2020-01-08 | 더블유.알. 그레이스 앤드 캄파니-콘. | Activator compositions, their preparation, and their use in catalysts |
JP6033322B2 (en) | 2012-09-25 | 2016-11-30 | 三井化学株式会社 | Transition metal compound, catalyst for olefin polymerization, and method for producing olefin polymer |
US9458257B2 (en) | 2012-09-25 | 2016-10-04 | Mitsui Chemicals, Inc. | Process for producing olefin polymer and olefin polymer |
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WO2020116368A1 (en) | 2018-12-04 | 2020-06-11 | 三井化学株式会社 | Resin composition containing 4-methyl-1-pentene copolymer, and film for capacitors |
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WO2022108971A1 (en) | 2020-11-23 | 2022-05-27 | Exxonmobil Chemical Patents Inc. | Toluene free supported methylalumoxane precursor |
WO2022108972A1 (en) | 2020-11-23 | 2022-05-27 | Exxonmobil Chemical Patents Inc. | Improved process to prepare catalyst from in-situ formed alumoxane |
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2007
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- 2007-05-02 EP EP07761717.3A patent/EP2013246B1/en active Active
- 2007-05-02 US US12/299,555 patent/US7960488B2/en active Active
- 2007-05-02 CN CN2007800160297A patent/CN101437858B/en active Active
- 2007-05-02 ES ES07761717T patent/ES2766851T3/en active Active
- 2007-05-02 PT PT77617173T patent/PT2013246T/en unknown
- 2007-05-02 WO PCT/US2007/067983 patent/WO2007131010A2/en active Application Filing
- 2007-05-02 CA CA2650483A patent/CA2650483C/en not_active Expired - Fee Related
- 2007-05-02 JP JP2009510042A patent/JP5775259B2/en active Active
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2016196334A1 (en) | 2015-06-05 | 2016-12-08 | Exxonmobil Chemical Patents Inc. | Single reactor production of polymers in gas or slurry phase |
WO2016197037A1 (en) | 2015-06-05 | 2016-12-08 | Exxonmobil Chemical Patents Inc. | Catalyst system comprising supported alumoxane and unsupported alumoxane particles |
WO2016196339A2 (en) | 2015-06-05 | 2016-12-08 | Exxonmobil Chemical Patents Inc. | Production of heterophasic polymers in gas or slurry phase |
EP3885373A1 (en) | 2015-06-05 | 2021-09-29 | ExxonMobil Chemical Patents Inc. | Production of heterophasic polymers in gas or slurry phase |
US11485815B2 (en) | 2018-04-11 | 2022-11-01 | Mitsui Chemicals, Inc. | 4-methyl-1-pentene polymer particle and method for producing 4-methyl-1-pentene resin |
WO2021247244A2 (en) | 2020-06-03 | 2021-12-09 | Exxonmobil Chemical Patents Inc. | Process for production of thermoplastic vulcanizates using supported catalyst systems and compositions made therefrom |
Also Published As
Publication number | Publication date |
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PT2013246T (en) | 2020-03-17 |
CN101437858A (en) | 2009-05-20 |
JP2009535495A (en) | 2009-10-01 |
WO2007131010A3 (en) | 2008-02-28 |
KR20090017568A (en) | 2009-02-18 |
HUE048053T2 (en) | 2020-05-28 |
WO2007131010A2 (en) | 2007-11-15 |
CA2650483C (en) | 2015-09-29 |
EP2013246A2 (en) | 2009-01-14 |
KR101461241B1 (en) | 2014-11-12 |
ES2766851T3 (en) | 2020-06-15 |
CA2650483A1 (en) | 2007-11-15 |
CN101437858B (en) | 2011-05-25 |
JP5775259B2 (en) | 2015-09-09 |
EP2013246B1 (en) | 2019-12-18 |
US20090088541A1 (en) | 2009-04-02 |
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